O-methyl-o-(2,2 dichloro-vinyl) phosphoric acid ester monochloride and method of preparation

ABSTRACT

Reacting O,O-dimethyl-0-(2,2-dichloro-vinyl)-phosphoric acid ester with phosphorus pentachloride, or with phosphorus trichloride and chlorine, e.g. at about 40*- 130* C., to form 0methyl-0-(2,2-dichloro-vinyl)-phosphoric acid ester monochloride, and reacting said monochloride with ammonia or a primary or secondary amine, e.g. at a temperature up to about room temperature, in the presence of an acid binding agent to form the corresponding O-methyl-O-(2,2-dichloro-vinyl)-phosphoric acid ester amide, some of which are known, and which possess arthropodicidal properties.

United States Patent 72] Inventors Wilhelm Sirrenberg Sprockhoevel; Wolfgang Behrenz; Ingeborg Hammann, both of Cologne, all of Germany [21] Appl. No. 687,162

[22] Filed Dec. 1, 1967 [45] Patented Dec. 7, I971 [73] Assignee Farbenfabriken Bayer Aktjengesellschaft Leverkusen, Germany [32] Priority Dec. 13, 1966 [3 3 Germany [54] 0-METHYL-0-(2,2 DICIILORO-VINYL) PHOSPHORIC ACID ESTER MONOCHLORIDE AND METHOD OF PREPARATION 5 Claims, No Drawings 52 us. (:1 260 957, 260/239 EP, 260/247, 260/247.7 A, 260/293 R,

511 161.01 A016 9/36, c071 9/20, CO7f9/24 [50] Field of Search 260/957, 986

[56] References Cited UNITED STATES PATENTS 2,947,773 8/1960 Allen 260/957 X 3,082,239 3/1963 Muhlmann et all 260/986 X 3,098,865 7/1963 Schimmelschmidt et al. 260/986 X 3,364,109 1/1968 Haering 260/957 X Primary Examiner-Charles B. Parker Assistant Examinen-Richard L. Raymond AltorneyBurgess, Dinklage and Sprung ABSTRACT: Reacting 0,0-dimethyl-0-(2,2-dichloro-vinyl)- phosphoric acid ester with phosphorus pentachloride. or with phosphorus trichloride and chlorine, e.g. at about 40-130 C., to form 0-methyl-0-(2,2-dichloro-vinyl)-phosphoric acid ester monochloride, and reacting said monochloride with am monia or a primary or secondary amine, e.g. at a temperature up to about room temperature, in the presence of an acid binding agent to form the corresponding O'methyI-O-(LZ- dichloro-vinyl)-phosphoric acid ester amide, some of which are known, and which possess arthropodicidal properties.

-METHYL-0-(2,2 DICHLORO-VINYL) PHOSPHORIC ACID ESTER MONOCHLORIDE AND METHOD OF PREPARATION The present invention relates to and has for its objects the provision for particular new methods of producing O-methyl- 0-(2,2-dichloro-vinyl)-phosphoric acid ester monochloride and o-methyl-0-(2,Z-dichloro-vinyl)-phosphoric acid ester amides, some of which are known, in two corresponding steps, using readily available starting materials whereby to attain outstanding yields, certain new 0-methyl-0-(2,2-dichloro-vinyl)-phosphoric acid ester amides which possess arthropodicidal properties, active compositions in the form of mixtures of such new compounds with solid and liquid dispersible carrier vehicles, and methods for using such new compounds in a new way especially for combating arthropods, with other and further objects of the invention becoming apparent from a study of the within specification and accompanying examples.

German Pat. Nos. 944,430 and 975,070 describe among other things the reaction of chloral with trialkylphosphites (A), which leads, in accordance with the following equation, to 0,0-dialkyl-0-(2,2-dichloro-vinyl)-phosphoric acid esters (HA) [Perkovs reaction}:

P-OR 0013-0110 in which R is an alkyl radical.

US. Pat. No. 2,744,128 as well as British Pat. Nos. 783,697, 784,985 and 784,986 also relate to the preparation of dichloro-vinyl esters of phosphoric acid from trialkylphosphites and chloral.

German Pat. No. 968,486 describes a process for the preparation of 0-(2-chloro-ethyl)0-(2',2-dichloro-vinyl)- phosphoric acid esters by reaction of ring-form phosphites with chloral.

The preparation of asymmetrical 2,2-dichloro-vinylphosphoric acid esters of the constitution (IlA) given above, in which the two radicals R are difi'erent, has been described in the literature (cf. for example US. Pat. Nos. 2,956,073 and 3,] 16,201).

The obtaining of 2,2-dichloro-vinyl-phosphoric acid ester amides (IA) by reaction of the appropriate 0,0-dialkylphosphorus acid ester N,N-dialkyl amides (B) with chloral by the method of Perkov, according to the following equation, is known (cf. V. S. Abramov and N. A. llyina, Doklady Akad. SSSR, Vol. 132, (1960), page 823, reported in Chemical Abstracts Vol. 54 (1960), column 22329g);

in which R, R and and R" are the same or different radicals,

preferably lower alkyl radicals.

radicals in such a manner that the asymmetrical phosphites desired are obtained in good yields. Instead, these compounds usually have to be obtained by isolating the O-alkylphosphorus acid dichloride which is first obtainedwhich isolation is usually effected by distillation-in order to separate it from the by-products which are formed simultaneously. In the case of the preparation of phosphorus acid diester amides with different lower alkyl radicals, additional difficulties arise because the boiling points of main product and byproduct differ too little. The desired products are, rather, only accessible in a further mixture. Moreover, in the case of the preparation of mixed phosphorus acid ester amides with different alkyl radicals of higher molecular weight, considerable additional difficulties often arise. In this case, the boiling point of the O-alkyl-phosphorus acid dichloride of higher molecular weight which is to be prepared in the first step may be so high that, at least when working on an industrial scale, a distillation purification of the aforesaid intermediate product is no longer possible or, on the other hand, a decomposition during distillation is to be feared. Poor yields and impure end products are the result.

It has now been found, in accordance with the present invention, that a versatile and smooth process may now be provided for the production in high yields. and high purity of 0- methyl-0-(2,2-dichloro-vinyl)-phosphoric acid ester amides, some of which are known, having the formula in which R and R each respectively is selected from the group consisting of hydrogen; alkyl having one to 12 carbon atoms; substituted alkyl having one to l2 carbon atoms which is substituted with a member selected from the group consisting of lower alkoxy, lower alkylmercapto, lower alkylamino, dilower alkylamino and one to three halo; alkenyl having two to 12 carbon atoms; cycloalkyl having five to eight ring carbon atoms; substituted cycloalkyl having fiv-e to eight ring carbon atoms and one to three lower alkyl substituents; phenyl lower alkyl; phenyl; and substituted phenyl which is substituted with one to three substituents selected from the group consisting of halo, nitro, cyano, thiocyano, lower alkoxy, lower alkylmercapto, lower alkyl sulfoxyl, lower alkyl sulfonyl, lower alkyl and mixtures of such substituents; with the proviso that R and R when taken together with the adjacent nitrogen atom form a heterocyclic ring system with one to three rings having three to 14 ring members and one to four hetero linking atoms selected from the group consisting of nitrogen, oxygen, sulfur and mixtures of such linking atoms; which comprises (a) reacting 0,0-dimethyl-0-(2,2-dichloro-vinyl)-phosphoric acid ester having the formula CHaO O P-O CH=C CI:

with phosphorus pentachloride at a temperature substantially between about 40 to C. to form the corresponding 0- methyl-0-(2,2-dichloro-vinyl)phosphoric acid ester monochloride having the formula PO-OH=C C12 C1 (IIb) and thereafter (b) reacting said monochloride with an amine reactant having the formula in which R, and R, are the same as defined above, in the presence of an acid binding agent to form the corresponding -methyl-0-(2,2-dichloro-vinyl)-phosphoric acid ester amide.

it has been furthermore found in accordance with the present invention that particular new 0-methyl-0-(2,2- l0 dichloro-vinyl)-phosphoric acid compounds having the formula CHaO O mil??? in which Z is selected from the group consisting of chloro and in which R, is selected from the group consisting of lower alkenyl, C cycloalkyl, phenyl and chloro-substituted phenyl, and R, is selected from the group consisting of hydrogen and lower alkyl, with the proviso that R, and R, when taken with the adjacent nitrogen atom form a heterocyclic ring system selected from the group consisting of ethylenimino, piperidyl and morpholyl, exhibit strong arthropodicidal, especially insecticidal and acaricidal, properties.

Surprisingly, all of the new amide compounds of the present invention are distinguished from the active compounds of analogous constitution and the same type of activity hitherto known, by a much greater effectiveness, with considerably lower toxicity to warm-blooded animals and to plants. The instant new amides therefore represent a genuine enrichment of the art.

Advantageously, the instant new process has been found to operate smoothly and to be capable of giving high yields with a high degree of purity of the product.

The extremely smooth and uniform course of the reaction according to the present invention could not be foreseen, since it was to be expected that a mixture of chlorination products would be obtained. in particular the fact that the dichloro-vinyl group remains intact during the action of phosphorus pentachloride is very surprising, since the latter adds onto molecules even under mild reaction conditions (cf. for example Chemisch Berichte", Vol. 63, page 1,158 (1930), Vol. 64, page 1,466 (1931), Vol. 66, page 278 (1933), Vol. 87, page 755 (1954), and Vol. 88, page 662 (i955) as well as US. Pat. No. 2,971,882). The possibility of the addition of halogen to the double bond in the 0,0- dimethyl-0-(2,2-dichloro-vinyl)-phosphoric acid ester (lla) has also been indicated in the literature (see G. Schrader Die Entwicklung neuer insektizider Phosphors'aure ester", 3rd Edition (1963), Verlag Chemie G.m.b.H., Weinheim, Berg strasse, page 46, ibidem further literature) and it is equally surprising that this result does not occur either in carrying out the present invention.

Compared with the methods which have hitherto been suggested for the preparation of substances of the type under discussion, the process of the present invention exhibits a series of remarkable advantages. First, the use of the phosphorus acid diester amides (B) which are difficult to prepare is avoided; instead, the basic starting material is 0,0-dimethyl-0- (2,2-dichloro-vinyl)-phosphoric acid ester (lla which is readily available even on an industrial scale, and from phosphorus pentachloride which is likewise obtainable commercially. Both steps of the process, in particular the chlorination step (a), proceed smoothly and can be readily carried out technologically. The 0rnethyl-0-( 2 ,Z-dichloro-vinyl phosphoric acid ester montxchlotkic (lib which is formed as novel and unobvious intermediate pmduct, and which it desired can be isolated from the reaction mixture, can at present not be prepared in any other way, since the L]- dichloro-vinyl alcohol which would be required as starting material for the known type of reaction with phosphorus oxychloride does not exist.

Furthermore, by means of the process of the present invention many new, technologically valuable 2,2-dichloro-vinylphosphoric acid ester amides (la) can be obtained, which either could not be obtained or could only be obtained with difiiculty by the methods described hitherto in the literature.

Besides its great breadth of application, the process of the present invention is also distinguished from earlier processes in that it can give better yields and purer products.

The course of the reactions of the process of the present invention is illustrated by the following equations:

As can be seen from the above equations, the first reaction gives only slightly volatile by-products, namely methyl chloride and phosphorus oxychloride.

As examples of primary and secondary amines, i.e., in addition to ammonia, corresponding to formula (llc) above, which may be used in accordance with the process of the present invention, there may be mentioned methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, n-amyl, isoamyl, ten.- amyl, 1,2,2-trimethylpropyl, pinacolyl, allyl, 2-methoxyethyl, 2-chloroethyl, 2,2,2-trichloroethyl, Z-ethylmercaptoethyl, 2- diethylaminoethyl, monomethylaminomethyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl and benzyl amines as well as the corresponding symmetrical and asymmetrical (i.e. mixed substituent) diamines; aromatic amines, for example aniline, lower N- alkyl-anilines such as methyland ethyl-aniline; 2-, 3- and 4- chloro-, 2,4-and 2,5-dichloro-, and 2,4,5- and 2,4,6-trichloroaniline; 2-chloro-4-methyl-, 3-chloro-4-methyl-, 3-methyl-4- cyclopentyl,

chloro-, and 2-chloro-4-tert.-butyl-aniline; 2-, 3- and 4- nitroaniline; 2- and 3-chloro-4-nitroaniline, and 2,5- and 3,5 dichloro4-nitroaniline; 2- and 3-methyI-4-nitroaniline, and 3- nitro-4-methylaniline; 2- and 3-methoxy-4-nitroaniline; 3- nitro-4-chloro-, 3-nitro4,6-dichloro-, and 2-nitro-4chloroaniline; 4-cyano-, 2- and 3-methyl-4-cyano-, 4-thiocyano-, and 2- and 3-methyl-4-thiocyano-aniline; 4-methyl-mercapto-, 4- rnethyl-sulphoxyl-, 4-methyl-sulphonyl-, 3-methyl-4-methylmercapto-, 3,5-dimethyl-4-methylmercapto-, 3-methyl-4- methyl-sulphoxyl-, and 3-methyl-4methyl-sulphonyl-aniline; and the like, and diphenylamine and its derivatives which are substituted in the nucleus in the manner stated above; and heterocyclic amines, for example ethylenimine, pyrrolidine, piperidine, morpholine, thiomorpholine, pyrrole, pyrazole, imidazole, 1,2,3- and l,2,4-triazole, l,2,3,4-and l,2,3,5- tetrazole, indole, carbazole, indazole, benzimidazole, purine, phenoxazine; and the like. i

The step (a) chlorination of the 0,0-dimethyl-O-(2,2- dichloro-vinyl)-phosphoric acid ester (lla) takes place expediently in the absence of solvents, while the step (b) reaction of the intermediate, -methyl-0-(2,2-dichloro-vinyl)- phosphoric acid ester monochloride (Ilb), with ammonia or the appropriate primary or secondary amine is carried out optionally, yet preferably, in the presence of inert organic solvents or diluents. As such, for either or both of steps (a) and (b), practically all inert organic solvents are suitable. Preferred solvents include hydrocarbons, such as especially aliphatic hydrocarbons, aromatic hydrocarbons and chlorinated aromatic hydrocarbons, and particularly lower aliphatic (lower alkyl) hydrocarbons, benzene hydrocarbons and chlorobenzene hydrocarbons, eg. benzine, benzene, toluene, xylene or chlorobenzene; ethers, especially aliphatic and cycloaliphatic ethers, and particularly lower aliphatic (lower alkyl) and cycloaliphatic ethers, e.g. diethyl, dibutyl, etc. ether, dioxan, tetrahydrofuran, etc., as well as low-boiling aliphatic ketones and nitriles, especially lower aliphatic ketones and nitriles, and particularly lower alkyl ketones and lower alkanoic acid nitriles, e.g. acetone, methylethyl, methylisopropyl, methylisobutyl ketone, etc., acetonitrile, propionitrile, etc.; and the like.

Moreover, the second step (b) is carried out preferably in the presence of acid-binding agents. Particularly suitable are tertiary organic amine bases, such as tertiary aliphatic, aromatic or heterocyclic amines, especially tertiary lower aliphatic (tri-lower alkyl), dilower aliphatic-phenyl (dilower alkyl-phenyl), diphenyl-lower aliphatic (diphenyl-lower alkyl) amines, and pyridine, e.g. triethylamine, diethylaniline, pyridine, etc., as well as alkali metal carbonates, cyanides and alcoholates (particularly alkylolates or alkanolates, including lower alkylolates or alkanolates, etc.), such as potassium, sodium, etc., carbonate, cyanide, methylate, ethylate, etc. Finally, it is also possible to use as acid-binding agent or acid accepter a 100 percent or more excess of the respective primary or secondary amine to be reacted in the second step of the instant process.

Both the first and the second steps of the process of the present invention can be carried out within fairly wide temperature ranges. The chlorination step (a) takes place, in general, at substantially between about 40 to 130 C., preferably 70 to l20 C., while in the second step (b) the reaction is generally carried out at low temperatures, i.e. up to about room temperature (substantially between about -1 0 to +20 C., preferably *5" to C.).

As can be seen from the equations stated above, for each mol of 0,0-dimethyl-(2,2-dichloro-vinyl)-phosphoric acid ester (lla) about 1 mol of phosphorus pentachloride is used and, in addition, for each mol of O-methyl-O-(Z,2-dichloro-vinyl)-phosphoric acid ester monochloride (Ilb) about 1 mol of ammonia or primary or secondary amine and 1 mol of acidbinding agent are used.

The chlorination step (a) takes place expediently in such a manner that the calculated amount of phosphorus pentachloride is introduced portionwise, with stirring, into the 0,0-dimethyl-0-(2,2-dichloro-vinyl)-phosphoric acid ester (Ila) and the reaction temperature increases gradually during the course of the addition until the above-mentioned maximum value is reached, while methyl chloride is evolved. Then, in order to complete the reaction, the reaction mixture is expediently heated for a further one-half to 3 hours and the phosphorus oxy-chloride which is formed as by-product is then distilled off under reduced pressure. The 0-methyl0-(2,2 -dichloro-vinyl)-phosphoric acid ester monochloride (iib) which remains behind is pure enough for the ensuing reaction. lf desired, it may, however, be distilled under reduced pres sure without appreciable losses of yield, and even be recovered per se,

According to a special form of carrying out the chlorination step (a) of the instant process, a mixture of the 0,0-dimethyl- 0-(2,2-dichloro-vinyl)-phosphoric acid ester (Ila) and approximately the equimolar amount of phosphorus trichloride is prepared and into this mixture there is introduced approximately half the calculated amount of molecular chlorine, i.e. gaseous chlorine.

The reaction of the 0-methiyl-0-(2,2-dichloro-vinyl)- phosphoric acid ester monochloride (Ilb) in amination step (b) takes place expediently in such a manner that a solution of the latter in a suitable solvent or diluent, e.g. of the foregoing type, is added dropwise, with stirring, to a mixture of the primary or secondary amine and the acid-binding agent (the reverse sequence may, however, also be chosen, especially where the amine reactant of formula. (lie) is gaseous ammonia or even liquid ammonia), and the reaction mixture is then maintained for a short time at room temperature.

The working up of the product may be effected in known manner by filtering off the precipitated salt, neutralizing the filtrate, drying it and evaporating the solvent, preferably under reduced pressure.

The 2,2-dichloro-vinyl-phosphoric acid ester amides (la) obtainable by the instant process remain behind in most cases in the form of colorless to slightly yellow colored oils, some of which can be distilled under greatly reduced pressure without decomposition and, in addition, can be unambiguously characterized on the basis of their refractive index, the thin layer chromatogram and the values for the elementary analysis. Sometimes, however, the instant amides are also obtained as crystalline substances with sharp melting point.

As already mentioned above, in accordance with the present invention all of the amide compounds of formula (la (most of which are new and unobvious compounds) have been found effective as insecticides or acaricides, i.e. arthropodicides; they possess a rapidly-commencing and long-lasting pesticidal effectiveness, with comparatively low toxicity to warm-blooded animals and comparatively low phytotoxicity. These 2,2-dichloro'vinyl-phosphoric acid ester amides (la can be used with success for the control of noxious sucking and biting insects, Diptera as well as mites, particularly in plant protection and the protection of stored goods, but also in the hygiene field.

To the sucking insects contemplated herein there belong, in the main, aphids (Aphidae) such as the green peach aphid (Myzus persicae), the bean aphid (Doralis fabae), the bird cherry aphid (Rhopalosiphum p adi.), the pea aphid (Macrosiphum pisi) and the potato aphid (Macrosiphum solanifolii), the currant gall aphid (Cryptomyzus korschelti), the mealy apple aphid (Sappaphis mali), the mealy plum aphid (Hyalopterus arundinis) and the cherry black-fly (Myzus cerasi); scales and mealybugs (Coccina), for example the oleander scale (Aspidiolus hederae) and the soft scale (Lecanium hesperidum) as well as the grape mealybug (Pseudococcus maritimus); thrips (Thysanoptera), such as Hercinothrips femoralis, and bugs, for example the beet bug (Piesma quadrata), the cotton bug (Dysdercus intermedium), the bed bug (Cimex lectularius), the assassin bug (Rhodm'us prolixus) and Chagas bug (Triatoma infeslans) and, cicadas, such as Euscelis bilobatus and Nephotettix bipunctatus; and the like,

In the case of the biting insects contemplated herein, there should especially be mentioned butterfly caterpillars (Lepidoptera) such as the diamond-back moth (Plutella maculipennis), the gipsy moth (Lymantria diapar), the browntail moth (Euprocu's chrysorrhoea) and tent caterpillar (Malacosoma neustria); the cabbage moth (Manestra brassicae) and the cutworm (Agrotis segetum), the large white butteifly (Pieris brassicae), the small winter moth (Cheimatobia brumata), the green oak tortrix moth (Tortrix viridana); the fall army worm (Laphygmafrugiperda) rugiperda) and cotton worm (Prodenia Iitura), the ermine moth (Hypanomeuta padella), the Mediterranean flour moth (Ephestia Kiihniella) and greater wax moth (Galleria mellonella); and the like. Also to be classed with the biting insects in this regard are beetles (Coleoptera), for example the granary weevil (Sitophilus granan'us Calandm granaria), the Colorado beetle (Leptinotarsa decemlineata), the dock beetle (Gastrophysa viridula), the mustard beetle (Phaedon cochleariae), the blossom beetle (Meligethes aeneus); the rasberry beetle (Byturus tomentosus), the bean weevil (Bruchidus Acanthoscelides obtectus), the leather beetle (Dermestesfrischi), the khapra beetle (Trogoderma granarium), the flour beetle (Tribolium castaneum), the northern corn billbug (Calandra or Sitaphilus zeamais), the drug-store beetle (Stegobium paniceum), the yellow mealwonn (Tenebrio molitor) and the saw-toothed grain beetle (Oryzaephilus surinamensis), and also species living in the soil, for example wireworms (Agriotes species) and larvae of the cockchafer (Melolontha melolontha); cockroaches; such as the German cockroach (Blatella germanica), American cockroach (Periplaneta americana), Madeira cockroach (Laucophaea or Rhyparobia madeirae), Oriental cockroach (Blatta orientalis), giant cockroach (Blaberus giganteus) and black giant cockroach (Blaberusfuscus) as well as Henschouledenia flexivina; further, Orthoptera, for example the house cricket (Acheta domesticus); termites such as the eastern subterranean termite (Reticulitermes flavipes) and Hymenoptem such as ants, for example the garden ant (Lasius niger); and the like.

The Diptera contemplated herein comprise essentially the flies, such as the vinegar fly (Drosophila melanogaster), the Mediterranean fruit fly (Ceratitis capitata), the house fly (Musca domestica), the little house fly (Fannie canicularis), the black blow fly (Pharmia aegina) and blue-bottle fly (Cal- Iiphora erythrocephala) as well as the stable fly (Stomoxys calcitrans); as well as gnats, for example mosquitoes such as the yellow fever mosquito (Aedes aegypti), the northern house mosquito (Culex pipiens) and the malaria mosquito (Anopheles stephensi).

With the mites (Acari) there are classed, in particular, the spider mites (Tetranychidae) such as the two-spotted spider mite (Tetmnychus telan'us Tetranychus althaeaeor Tetranychus urticae) and the European red mite (Paratetranychus pilosus Panonychus ulmi), blister mites, for example, the current blister mite (Eriophyes ribis) and tarsonemids, for example the broad mite (Hemitnrsonemus Iatus) and the cyclamen mite (Tarsonemus pallidus); finally, ticks, such as the relapsing fever tick (Ornithodorus moubata); and the like.

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with diluents or extenders, i.e. dispersible carrier vehicles, such as solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granulates, etc. These are prepared in known manner, for instance by extending the active compounds with dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g. surface-active agents, including emulsifying agents and/r dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents (cf. Agricultural Chemicals, March I960, pages 35-38). The following may be chiefly considered for use as carrier vehicles for this purpose: dispersible liquid diluent carriers, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, etc.), halogenated, specially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc.), paraffins (e.g. petroleum fractions), (e.g. aliphatic hydrocarbons (e.g. methylene chloride, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, etc.), amines (e.g. ethanolamine, etc.), ethers, ether-alcohols (e.g. glycol monomethyl ether, etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sulfoxide, etc.), ketones (e.g. acetone, etc.), and water, as well as dispersible finely divided solid carriers, such as ground natural minerals (e.g'. kaolins, alumina, silica, chalk, i.e. calcium carbonate, talc, kieselguhr, etc.) and ground synthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g. alkali silicates, etc.); whereas the following may be chiefly considered for use as carrier vehicle assistants, e. g. surface-active agents, for this purpose; emulsifying agents, such as nonionic and anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfonates, aryl sulfonates, etc., and especially alkyl arylpolyglycol esters, magnesium stearate, sodium oleate, etc.); and dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other acaricides, insecticides, fungicidds, herbicides, bactericides, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granulates which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 0.1-95 percent, and preferably 0.5- percent by weight, of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.0000l-20 percent, preferably 0.0l-5 percent, by weight of the mixture. Thus, the present invention contemplates overall compositions which comprise mixtures of a dispersible carrier vehicle such as (l a dispersible carrier solid, or (2) a dispersible carrier liquid preferably including a carrier vehicle assistant, e.g. surface-active agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.0000lpercent, and preferably 0.01-95 percent by weight of the mixture.

In particular, the present invention contemplates methods of selectively controlling or combating pests, e.g. arthropods, i.e. insects and acarids, and more particularly, methods of combating at least one of insects and acarids which comprise applying to at least one of correspondingly (a) such insects, (b) such acarids, and (c) the corresponding habitat, i.e. the locus to be protected, a correspondingly combative amount, i.e. an anthropodicidally, especially insecticidally or acaricidally, effect amount of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, gasifying fumigating, scattering, dusting, watering, sprinkling, pouring and the like.

It will be realized, of course, that the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.

The unexpected superiority as well as the outstanding activity of the instant compounds when used against a multiplicity of pests and animal parasites is illustrated without limitation by the following examples.

EXAMPLE 1 EXAMPLE 2 Phaedon larvae test Drosophila Test Solvent 3 parts by weight acetone 5 Solvent 3 pans by weight acetone Emulsifier l part by weight alkylaryl polyglycol Emulsifler 1 part by weight alkylaryl polyglycol ether ether.

To produce a suitable preparation of the particular active compound, 1 part by weight of such active compound is mixed To produce a preparanon the pamculaf i with the stated amount of solvent containing the stated 1 Pan by we'ght of such acme "P" ls mlxed amount of emulsifier, and the concentrate obtained is diluted the Stated ,amoum of comammg i gated with water to the desired final concentration. amount of emulslfier, and the resulting concentrate is diluted Cabbage leaves (Brassica oleracea) are sprayed with this Water tome f preparation of the given active compound until dripping wet P the Preparatlon of the glvem P P l and then infested with mustard beetle larvae (Phaedon P R'P to filter Paper dlsc of 7 hamstercochlean'aey The wet dISC is placed in a-glass vessel containing vinegar After the period of time stated in the following table, the 0188 (Drvwphila g s r) and covered with a glass plate. degree of destruction of the pests is determined and expressed After the specified Perlod of the destruction f as a percentage; 100 percent means that n and 0 percent mined as apercentage: 100 percent means that all the fires are means that oneY f the beetle larvae are killed 20 k1lled;0 percent means that none of the flies are killed.

The particular active compounds tested, their concentra- The particular active compounds tested, their contractions, tions, the evaluation time and the experimental results obthe evaluation time and the degree of destruction obtained tained can be seen from the following table 1: can be seen from the following table 2.:

TABLE 1 Concentration Degree of of active. destruction compound in in percent Active compound (constitution) percent. after 3 days (11130.... CHSO o 0.1 100 l 0, 01 100 OCH=C C12 0.001

( CH3)2CHN H (IV1) C1130 0 0.1 ll 0. 01 100 P 0 O CH: C C 1:

CHz=CH-CHzNH (V1) CHaO O 0.1 100 ll 0. 01 100 CH2 PO-CH=C C12 0001 60 N CH2 (Vlai) crno 0 0.1 100 H 0.01 100 P- O CH: C C1:

CH3N H 1) CHSO 0 0.1 100 0. 01 100 P O CH: 0 C12 TABLE 2 Concentration Degree of of active destruction compound in in percent Active compound (constitution) percent after 24 hours (X1) CHaO O 0. 1 100 \ll 1 0.01 100 m OCH CC 2 0.001 100 N (V9) CHaO O 0.1 100 0.01 100 7 CH2 POCH=CC12 0.001 100 /N CH2 W132)..." CHaO O U. 1 100 \ll 0.01 100 -OGH==O C11 0.001 100 GHQ-NH (VII2). CHaO O 0.1 100 0.01 100 P OCH=C Ch NH W EXAMPLE 3 a 7 Emulsifier l part by weight alkylaryl polyglycol ether. Myzus Test (contact action) Solvent 3 parts by weight acetone Emulsifi" I pm by weigh alkylaryl polyglycol To produce a suitable preparation of the particular acti e ether.

To produce a suitable preparation of the particular active compound 1 part by weight of such active compound is mixed compound, 1 part by weight of such active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier and the resulting concentrate is diluted with water to the desired final concentration.

Bean plants (Phaseolus vulgaris), which have a height of apwith the stated amount of solvent containing the stated amount of emulsifier and the resulting concentrate is diluted proximately are p y with the Preparation of with water t th d i d fi l concentration the given active compound until dripping wet. These bean Cabbage plants (Brassica oleracea) which have been heavily Plants are heavily Infested wlth P' mites (Telmnychus infested with peach aphids (Myzus persicae) are sprayed with lelarius) all stages of p f the preparation of the given active compound until dripping 40 After the Speclfied P of lhe effectiveness of the wet. preparation of the given active compound is determined by After the specified period of time, the degree of d t ti n counting the dead mites. The degree of destruction thus obis determined as a percentage: 100 percent means th ll h tained is expressed as a percentage: I00 percent means that all aphids are killed whereas 0 percent means that n f th the spider mites are killed whereas 0 percent means that none aphids are killed. of the spider mites are killed.

The particular active compounds tested, their concentra- The particular active compounds tested, their concentrations, the evaluation time and the results obtained can be seen tions, the evaluation time and the results obtained can be seen from the following table 3: from the following table 4:

TABLE 3 Concentration Degree of of active destruction compound in in percent Active compound (constitution) percent after 24 hours (IIIa3) 01130 O 0. 1 100 ll 0. 01 P O CH: C C12 (CHa)2CH-NH (IVs) CHaO O 0. 1 0, 01 95 OCH=C C12 CH2=CH--OHzNH (Va) (EH30 0 0. 1 100 0.01 99 CH: POCH=C C12 N l CH2 (VIa3).. CHaO 0 0.1 100 H 0.01 on P OCH= C C12 CHaNH EXAMPLE 4 Tetranychus Test 75 Solvent 3 parts by weight acetone TABLE 4 Concentration Degree of of active destruction compound in in percent Active compound (constitution) percent after 48 hours (IIIai)- H30\fi) O. 1 100 P--0CH=C C12 (OHa):CH-NH 100 (IVal)..... OH3O\fi 0.1

P- 0-GH=C C1:

CH:=CH-CH2NH (VIa4) 01130 O 0. 1 100 II 0.01 so P- O-CH=C C12 CH3NH EXAMPLE 5 EXAMPLE 6 2O Rhopalosiphum Test (systemic action) loo Test for Dlpmra Test insects: House flies (Musca domestica) Solvent 3 parts by weight acetone S l Acetona Emulsifier 1 part by weight alkylaryl polyglycol ether. To produce a suitable preparation of the particular active compound, I part by weight of such active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier and the resulting concentrate is diluted with water to the desired final concentration.

Oat plants (Avena saliva) which have been strongly infested 1 with oat aphids (Rhopalosiphum padi) are watered with the preparation of the given active compound so that the preparation penetrates into the soil without wetting the leaves of the oat plants. The active compound is taken up by the cat plants from the soil and thus reaches the infested leaves.

After the specified period of time, the degree of destruction is determined as a percentage: 100 percent means that all the aphids are killed whereas 0 percent means that none of the aphids are killed.

The particular active compounds tested, their concentrations, the evaluation time and the results obtained can be seen from the following table 5:

TABLE 6 2 parts by weight of the particular active compound are dissolved in 1000 parts by volume of solvent. The solution so obtained is diluted with further solvent to the desired final lower concentration.

2.5 ml. of the solution of the given active compound are pipetted into a Petri dish. On the bottom of the Petri dish there is a filter paper with a diameter of about 9.5 cm. The petri dish remains uncovered until the solvent has completely evaporated. The amount of active compound per square meter of filter paper varies with the concentration of the solution of active compound used. About 25 test insects are then placed in the Petri dish anditis covered with a glass lid.

The condition of the test insects is continuously observed. The time which is necessary .for a I00 percent knockdown effect is determined.

The test insects, the particular active compounds tested, their concentrations and the period of time at which there is a 100 percent knockdownefi'ect can be seen from the following table 6:

Concentration Degree oi of active destruction compound in in percent Active compound (constitution) percent after 4 days mm... C1130 0 0.1' 100 H 0. 01 100 P OCH= 0 C12 (CHa)2CHNH (IVs) (EH30 O 0.1 100 0 01 P--OCH=CC12 CH2= CHCHz-NH (VIIIaz) CHaO\fi) 0.1

P--O-CH=CC12 (C2H5)2N (IXz)... CHsO\(H) 0.1 100 P --OCH=C Clz H N (X2) CH3 O\fi 0. 1 100 P -O-CH=CC12 CH? P-OCH=CC12 /N CH2 (VIas).. 01130 O 0. l. 100 II 0. 01 100 TABLE Concentration of active LTton in compound in minutes Active compound (constitution) percent or hours (IIIea).. CH3O O 0. 2 l

1] 0. 02 40 PO-OH=C C12 0.0002 105 0.0002 8' (0 H3) 2CH-NH (VIIIa 0 H30 0 0. 2

\ ll 0. 02 190' =5o% POCH=CC1: 0.002 8 OX OHQO O 0.02 25' 0. 02 so =50% P-O-CH=C 012 0.012 8 (X CH O\0 0 (2y2 0 POCH=OC12 0 002 130' 0 0002 s (Vs) CHaO 0 0. ll 0. 02 15' CH; POCH=C C12 0.002 60 CVO)---" CHaO\(") POCH=C 012 00002 220' CH2=C H- CH2 EXAMPLE 7 t EXAMPLE 8 LT Test for Diptera LD Test Test insects: Yellow fever mosquitoes (Aedes aegypti Solvent: Acetone.

Test insects: Oriental cockroaches (Blatta orienlalis) Solvent: Acetone.

Two parts by weight of the particular active compound are 40 Two parts by weight of the particular active compound are dissolved in 1000 parts by volume of solv n Th i n so dissolved in 1000 parts by volume of the solvent. The solution Obtained i il ed Wi h f rther Solvent 10 the desired fi so obtained is diluted with further solvent to the desired final lower concentration. concentration.

2.5 ml. of the solution of the given active compound are 2.5 ml. of the solution of the given active compound are p p into a Petri dishon the bottom of the Petri dish ere pipetted into a Petri dish. On the bottom ofthe Petri dish there is a filter paper with a diameter of about 9.5 cm. The Petri dish i a filt r paper with a diameter of about 9.5 cm. The Petri dish remains uncovered until the solvent has completely r ain un overed until the solvent has completely evaporated. The amount of active compound per square evaporated. The amount of active compound per square meter of filter paper varies with the concentration of the sclumeter of filter paper varies with the concentration of the solution of active compound e AbOut 25 e insects are tion of active compound used. About 25 test insects are then placed in the Petri dish and it is covered with a glass lid. laced in the Petri dish and it is overed with a glass lid.

The condition of the test insects is continuously observed. The condition of the test insects is observed after l and 3 The time which is necessary for a 100 percent knockdown efdays from the commencement of the experiments. The feet is determined. knockdown effect is determined as a percentage, and this is The test insects, the particular active compounds tested, stated as LD their concentrations and the period of time at which there is a The particular active compounds tested, their concentral00 percent knockdown effect can be seen from the following tions and the results obtained can be seen from the following table 7: table 8:

TABLE 7 Concentration of active compound LTiao in Active compound (constitution) in percent minutes (IIIa1) CHzO O 0.2 0. 02 so -OCH=C Cl: 0. 002

(CHa)2CH-N (VIIIa 011 0 O 0. 2 60 I 0.02 60 =90% -o-cH=oou 0.002 l 2 ls)2N (IX|)-. CHaO O 0.2 60

\ll 0. 02 so =s0% POCH=C Cl: 0.002 180 TABLE 7 Concentration of active compound LIwo in Active compound (constitution) in percent minutes (X4) CHaO O 0. 2 c on o 01 0 08; 138 2 O N (Va) CHaO O 0.2 00 0.02 00 CH5 O-GH==C C12 0. 002 00 =80% (IV1) CHsO 0 00b: -O-CH=C on 0. 002 180 0. 0002 180 CH2==GHCH2NH TABLE 8 Concentration Knock-down of active efllect (LDroo) compound in percent Active compound (constitution) in percent after 72 hrs.

(IIIas)- CHsO O 0.2 10 0. 02 100 --OCH=C 012 0.002 60 (CHahCH-NH (VIIIar)- CHaO O 0. 2 100 0.02 00 --O-GH=C Ch 2Hr)2N (IX5) CHaO 0.2 100 i'-OCH=C C12 H N (X5) CH3 O\(") 0. 2 100 P-OCH=C C12 6 (V1)-... CHaO O 0.2 100 \ii 0. 02 100 CH2 OCH=C C12 0.002 l (IVs) CHaO\(l) 006; 1g?) 1 -o-oH.- o o1. OH =CH-CHz-NH EXAMPLE 9 EXAMPLE 1.0 LD test Mosquito larvae test Test insects: Granary weevils (Sitophilus granarius) Solven. Acetone Tent insects: Yellow fever mosquito larvae (Aedes 1') Two parts by weight of the particular active compound are 50mm. 12.11,. weigh, among dissolved in 1000 parts by volume of the solvent. The solution Emulsifier: l part by weight so obtained is diluted with further solvent to the desired final g g' lmlyglyw' concentration.

2.5 ml. of the solution of the given active compound are pipetted into a Petri dish. On the bottom of the Petri dish there is a filter paper with a diameter of about 9.5 cm. The Petri dish remains uncovered until the solvent has completely evaporated. The amount of active compound per square meter of filter paper varies with the concentration of the solution of active compound used. About 25 test insects are then placed in the Petri dish and it is covered with a glass lid.

The condition of the test insects is observed after i and 3 days from the commencement of the experiments. The knockdown effect is determined as a percentage (LD The particular active compounds tested, their concentrations, the test insects and the results obtained can be seen from the following table 9:

To produce a suitable preparation of the particular active compound, two parts by weight of such active compound are dissolved in 1000 parts by volume of the solvent containing the amount of emulsifier stated above. The solution thus obtained is diluted with water to the desired final lower concentrations.

The aqueous preparations of the given active compounds are placed in glass vessels and about 25 mosquito larvae are then placed in each glass vessel.

After 24 hours, the degree of destruction is determined as a percentage. percent means that all the larvae are killed. 0 percent means that no larvae at all are killed.

The particular active compounds tested, their concentra tions, the test insects and the results obtained can be seen from the following table 10:

TABLE 9 Concentration Knock-down of active ofloct (LD compound in percent Active compound (constitution) in percent aitor 72 hrs. (IIIao). p. CHrO O 0. 2 100 \IIL 0. 02 I00 --0-CH=C C12 CH3) rCHN H (VIIIM) CHaO O 0. 2 100 0. 02 -0--CH=C Cl:

(C 2H5) 2N (X0) CHaO O 0. 2 100 \il 0. 02 00 -0-CH=C Cla 6 a) CHrO O 0. 2 100 Ill! 0. 02 100 CHz\ -OCH=C Ch I CH (IV'o) CHaO O 0.2 100 0. 02 100 0--CH=C Oh 0.002 CH2=CHCH2NH TABLE 10 Concentration Degree of of active comdestruction Active compound (constitution) pound in percent in percent (IIIa1u) CH3() 0 0.001 100 ll 0. 0001 80 P OCH=C 011 (C Ha)1 C H-NH X). CHaO\fi) 0.001 100 l O-CII=C C11 (X1) CHQO 0 0.001 100 II 0. 0001 30 O/ N/PO- Cll=-CCl2 (Va) CHaO O 0.001 100 ll 0. 0001 100 CH; /P0CII=C 011 (IV1o). CHaO O 0.001 100 0. 0001 100 The following further examples illustrate without limitation the production process of the present invention:

EXAMPLE ii a. 0-methyl-0-(2,2-dichlorovinyl)-phosphoric acid ester chloride CHsO fi) PO-CH=C C12 To 221 g. 0,0-dimethyl-0-(2,2-dichlorovinyl) phosphoric acid ester (lla) are added 209 g. phosphorus pentachloride, portionwise at such a rate that the preceding portion has in each case largely dissolved or reacted. This is readly discernible by the reduction of solid phosphorus pentachloride in the reaction mixture. During the said addition the temperature of the mixture is increased from 70 C. initially to l l0 to 120 C.

and, after completion of the addition, the mixture is further stirred for 1 hour at 120 C. The phosphorus oxychloride formed as byproduct is distilled off under reduced pressure The 0-methyl-0-(2,2-dichlorovinyl)-phosphoric acid ester monochloride (llb) comes over at 84 to C./l mm. Hg. and possesses the refractive index n,,l.4730. The yield is I70 g. (75 percent of the theory).

To a mixture of 64 g. isopropyiamine and 101 g. triethylamine in l liter benzene, there is added dropwise at C. a solution of 225.6 g. 0-methyl-0-(2,2-dichlorovinyl)- phosphoric acid ester chloride (llb). After completion of the addition, the mixture is further stirred for l hour at room temperature. The precipitated salts are then filtered off with suction and the filtrate is washed until there is a neutral reaction. The organic layer is then dried over sodium sulfate and the solvent is distilled off. The residue comes over at a pressure of 0.3 mm. Hg. at 114 C. After distillation, the O-methyl-N- isopropyl-0-(2,2-dichlorovinyl)-phosph0ric acid ester amide (lll) possesses a refractive index of n =l .4676. The yield is 147 g. (59 percent ofthe theory).

ANALYSIS Calculated for c li o Cl NP (molecular weight 248.06)

Cl 28.59% N5.65% P |2.4s% Found 012mm, N5.83% Pl2.5l%

EXAMPLE 12 According to the methods described above under example ll(b), there can also be obtained the 2,2 dichlorovinylphosphoric acid ester amides of the general constitution and tert.-butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and the like, especially C alkyl, more especially lower alkyl, and particularly C alkyl;

straight and branched chain alkenyl having two to l2 carbon atoms such as vinyl, a-alkyl (prop-Z-enyl), B-allyl (lmethyl-vinyl), 'y-allyl (prop-l-enyl), but-3-enyl, but-Z-enyl (crotyl), but-l-enyl, isobutenyl (Z-methyl-prop-l-enyl), methallyl (2-methyl-prop-2-enyl), pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, and the like, especially C alkenyl, more especially lower alkenyl, and particularly C alkenyl;

such alkyl having one to 12 carbon atoms such as methyl to dodecyl inclusive, and the like, as defined above, which is substituted with lower alkoxy such as methoxy, ethoxy, nand iso-propoxy, n-, iso-, sec.- and tert.-butoxy, and the like, especially C alkoxy;

lower alkylmercapto such as methyl to tert.-butyl inclusive, and the like, as defined above, -mercapto, especially C alkylmercapto;

lower alkylamino such as methyl to tert.-butyl inclusive, and the like, as defined above, -amino, especially C alkylamino;

dilower alkylamino such as diand mixed- (same or different) methyl to tert.-butyl inclusive, and the like, as defined above, -amino, especially di-C alkylamino; or

One to three halo such as chloro, bromo, iodo and/or fluoro, especially one to three chloro, and more especially chlorosubstituted C alkyl;

cycloalkyl having five to eight ring carbon atoms such as cyclo-pentyl, hexyl, heptyl, octyl, and the like, especially C cycloalkyl, and more especially cyclohexyl;

such cycloalkyl having five to eight carbon atoms which is substituted with one to three lower alkyl such as methyl to tert.-butyl inclusive, and the like, as defined above, especially C alkyl;

phenyl lower alkyl such as phenyl substituted-methyl to tert.-butyl inclusive, and the like, as d-efined above, especially Physical properties Yield Refractive (percent B.P. or M.P. index of the Hi R2 (O.) [1m theory) (Vlag) CH H LB.P.=102 1 1.4713 54. 5 (W11) CHz=GHCHz-- H B.P.=145 3 1.4845 43.5

(VH3) H M.P.=64 51.5

(VIIIa1)... CzH C2H5- 13.1. 4 1. 4659 46. 0 (XIIa1) 7LC H nCaH B.P.=103105 1.4638 34. 5 (XIIIa1) nO Hg TLC4Hn 1.4615 76.0

(XIV1)... Q CH: 1.5472 90.0

(V10) l (]J B.P.=96 I 1. 4831 50. 0

CHz- H;

(1X7) I I B.P. =-115 1. 4881 45. 0

(1H2 CH: C H2 C H2 C H2 (X l l B.P.= 1.4878 33.0

CH2 CH H2 OCH2 0.01 mm. 2 my 3 0.1 mm. 4 0.05 mm.

Advantageously, in accordance with the present invention, in the foregoing formulas:

R, and R, each respectively represents (same or different) hydrogen;

straight and branched chain alkyl having one to 12 carbon atoms such as methyl, ethyl, nand iso-propyl, n-, iso-, sec.-

phenyl C alkyl;

phenyl; substituted phenyl which is substituted with one to three halo as defined above, especially chloro, and more especially monochloro;

nitro;

cyano; thiocyano (-SCN); lower alkoxy as defined above, and especially C, alkoxy; lower alkylmercapto as defined above, and especially C alkylmercapto;

lower alkylsulfoxyl such as methyl to tert.-butyl inclusive,

and the like, as defined above, -sulfoxyl, and especially C, al-

kylsulfoxyl (-alkyl-SO);

lower alkylsulfonyl such as methyl to tert.-butyl inclusive, and the like, as defined above, -sulfonyl, and especially C,., alkylsulfonyl (-alkyl S0,); and/or lower alkyl such as methyl to tert.-butyl inclusive, and the like, as defined above, and especially C H alkyl;

with the proviso that R, and R, when taken with the adjacent nitrogen atom form a heterocyclic ring system with one to three, e.g. fused, n'ngs having a total of three to 14 ring members and one to four hetero linking atoms such as nitrogen, oxygen and/r sulfur including ethylenimino, pyrrolidyl, piperidyl, morpholyl, thiomorpholyl, pyrrolyl, pyrazolyl, imidazolyl, l,2,3-, l,2,4-, etc., -triazolyl, l,2,3,4- and l,2,3,5-tetrazolyl, indolyl, indazolyl, benzimidazolyl, purinyl (purine), carbazolyl, phenoxazino, etc., and the like, and especially ethylenimino, piperidyl and morpholyl.

Preferably, R, and R, each respectively is (same or different) hydrogen, C, alkyl, C, alkenyl, C cycloalkyl, phenyl or halophenyl, with the proviso that R, and R when taken together with the adjacent nitrogen atom form ethylenimino, piperidyl or morpholyl.

More particularly, R, is lower alkyl, lower alkenyl, C cycloalkyl, phenyl or chloro-substituted phenyl, and R, is hydrogen,'lower alkyl, lower alkenyl, C cycloalkyl, phenyl or chloro-substituted phenyl, with said proviso that R, and R, when taken together with the adjacent nitrogen atom form ethylenimino, piperidyl or morpholyl.

With respect to the new and unobvious compounds of the present invention, these include those in which R, is C, alkenyl, C cycloalkyl, phenyl or halophenyl, and R, is hydrogen or C, alkyl, with said proviso that R, and R, when taken together with the adjacent nitrogen atom form ethylenimino, piperidyl or morpholyl. In these new compounds, preferably, R, is lower alkenyl, C cycloalkyl, phenyl or chloro-substituted phenyl, and R, is hydrogen or lower alkyl, with said same proviso. In particular, such new compounds contemplate those in which R, is lower alkenyl, C cycloalkyl, phenyl or chloro-substituted phenyl, and R, is hydrogen when R, is lower alkenyl, C cycloalkyl or chloro-substituted phenyl while R, is lower alkyl when R, is phenyl, with said same proviso.

The intermediate, 0-methyl-0-(2,2-dichloro-vinyl)- phosphoric acid ester monochloride (llb), ie. where Z in formula (laa) is chloro, is also contemplated as a new and unobvious compound in accordance with the present invention.

It will be realized that all of the foregoing compounds contemplated by the present invention possess the desired selective pesticidal, especially arthropodicidal, i.e. insecticidal or acaricidal, properties for combating insects and acarids, and

that such compounds have not only a very slight toxicity toward warm-blooded creatures, but also a concomitantly low phytotoxicity,

As may be used herein, i.e. both in the specification and claims, the terms arthropod, arthropodicidal" and arthropodicide" contemplate specifically both insects and acarids. Thus, the insects and acarids may be considered herein collectively as arthropods to be combated in accordance with the invention, and accordingly the insecticidal and/or acaricidal activity may be termed arthropodicidal activity, and the concomitant combative or effective amount used will be an arthropodicidally effective amount which in effect means an insecticidally or acaricidally effective amount of the active compound for the desired purposes.

It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention which is to be limited only by the scope of the appended claims.

What is claimed is:

1. 0-methyl-0-(2,2-dichloro-vinyl)-phosphoric acid ester monochloride having the formula CHaO O P() CHzC C12 CHaO 2. Process which comprises reacting 0,0-dimethyl-0-(2,2- dichloro-vinyl)-phosphoric acid ester having the formula CHaO 0 with phosphorus pentachloride at a temperature substantially between about 40-l 30 C. to form the corresponding 0- methyl-0-(2,2-dichloro-vinyl)-phosphoric acid ester monochloride having the formula 3. Process according to claim 2 wherein said reaction is carried out at a temperature substantially between about 70 to C. using substantially equimolar amounts of said 0,0- dimethyl-0-(2,2-dichloro-vinyl)-phosphoric acid ester and said pentachloride.

4. Process according to claim 2 wherein said monochloride is isolated from the resulting reaction mixture.

5. Process according to claim 2 wherein said 0,0-dimethyl- 0-(2,2-dichloro-vinyl)-phosphoric acid ester is admixed with a substantially equimolar amount of phosphorus trichloride in place of said phosphorus pentachloride and substantially about one-half of the calculated corresponding molar amount of molecular chlorine is reacted therewith at said temperature to form said monochloride.

2 233 I wmwzn STA'IES PATENT OFFICE CETH ICATE We CURREQTKON Patent NO- 3626036 Dated em er'h 1971 Inyentofls) Wilhelm Sirrenberg, et a1},

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. 1 line 7 "o niethyl" should be Ormethyl 0610 4 line 14- "Omethy1 should b G-methyl C010 4, first formula (Ha) w w mm C1 shod be P81 second formula. (11b) Cole 5 line 30 should be 1 1 M COL 7 6 1 "althagaeor" hould be althaeae ar -UN1'IED'STA'1ES PATENT QFFKCE @ER'HFICATE 0F CURREQ'HGN Parent No. 3626036 mired Decembr 7 1971 1yntor(5) Wilhelm Sirrenberg e t a1;

It is certified that error appears in the above-idenltified patent and that said Letters Patent are hereby corrected as shown below:

001. 15 w formula 1x "00 02." should be mz @0012 should be 000m C01. 15 last formula of Table 6 (formula 1V f.

0.,0002" next tolasr. figure in next to last column should Be flo 002- r w 'H gm am C should be Elma}.

I "owalkyl" should be a allyl 'KSEAL Attestz' EDWARD MrFLETC2E1?! ,m ROBERT CY'QTTSCM Attastmg Offiger Geissiomer' of Patants L I a I r 

2. Process which comprises reacting 0,0-dimethyl-0-(2,2-dichloro-vinyl)-phosphoric acid ester having the formula
 3. Process according to claim 2 wherein said reaction is carried out at a temperature substantially between about 70* to 120* C. using substantially equimolar amounts of said 0,0-dimethyl-0-(2, 2-dichloro-vinyl)-phosphoric acid ester and said pentachloride.
 4. Process according to claim 2 wherein said monochloride is isolated from the resulting reaction mixture.
 5. Process according to claim 2 wherein said 0,0-dimethyl-0-(2, 2-dichloro-vinyl)-phosphoric acid ester is admixed with a substantially equimolar amount of phosphorus trichloride in place of said phosphorus pentachloride and substantially about one-half of the calculated corresponding molar amount of molecular chlorine is reacted therewith at said temperature to form said monochloride. 